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At least 37 records · Page 2

A possible role of fluctuating clay-water systems in the production of ordered prebiotic oligomers

A model is proposed for the intermediate stages of prebiotic evolution, based on the characteristics of the adsorption and condensation of amino acids and nucleotides on the surface area of clay minerals in a fluctuating environment. Template replication and translation of adsorbed oligonucleotides and catalytic effects by peptide products on further condensation are proposed, due to specific properties of hypohydrous clay surfaces as well as the biomolecules themselves. Experimental evidence supports some of the proposed interactions, and all of them can be tested experimentally.

Lahav, N.↗

Constraining the Hydration of Clay Minerals and Abundances of Amorphous Phases in Gale Crater, Mars

Both water and organic matter are required for the development and persistence of life. Phyllosilicates (clay minerals) have high surface areas that easily sorb water and organic matter. The Curiosity rover has investigated several hundred meters of stratigraphy in Gale crater, including where clays were detected from orbit. Previous results have suggested that subsurface hydration is greatest in units with the most abundant clays, suggesting that these minerals may be hydrated. Organics have also been found throughout Gale crater. Smectites are the most common and abundant phyllosilicates in Gale crater samples and can expand and sorb water and organics in interlayer sites. The most common organic sorption processes on Earth typically involve water or hydroxyl, so hydrated phyllosilicates are good candidates for organic preservation. Using newly derived subsurface hydration results with previously published mineralogy and geochemistry, we derived modeled constraints on the abundances of hydrated amorphous phases, “excess” water, and “excess” cations. These “excess” phases are not accounted for by published crystalline phase abundances or by amorphous phases constrained here. We found correlations between smectites and both “excess” water and “excess” cation abundances, indicating that smectites in Gale crater are hydrated and that cation bridging could be a mechanism for sorption of organics. Our results also show the persistence of amorphous sulfates, opal-A, and volcanic or impact glass, which indicate low water-rock interactions. Increased abundances of sulfates and glass in stratigraphically higher samples may indicate lower water availability and environmental aridification during the time these units were being deposited.

58 GEOSCIENCES↗

Dose- and Ion-Dependent Effects in the Oxidative Stress Response to Space-Like Radiation Exposure in the Skeletal System

Exposure to space radiation may pose a risk to skeletal health during subsequent aging. Irradiation acutely stimulates bone remodeling in mice, although the long-term influence of space radiation on bone-forming potential (osteoblastogenesis) and possible adaptive mechanisms are not well understood. We hypothesized exposure to ionizing radiation impairs osteoblastogenesis in an ion-type specific manner, with low doses capable of modulating expression of redox-related genes. 16-week old, male, C57BL6/J mice were exposed to low linear-energy-transfer (LET) protons (150 mega electron volts per nucleon) or high-LET (sup 56) Fe ions (600 mega electron volts per nucleon) using either low (5 or 10 centigrays) or high (50 or 200 centigrays) doses at NASAs Space Radiation Lab at Brookhaven National Lab (NSRL/BNL). Tissues were harvested 5 weeks or 1 year after irradiation and bones were analyzed by microcomputed tomography for cancellous microarchitecture and cortical geometry. Marrow-derived, adherent cells were grown under osteoblastogenic culture conditions. Cell lysates were analyzed for select groups by RT-PCR (Reverse Transcription-Polymerase Chain Reaction) during the proliferative phase or the mineralizing phase, and differentiation was analyzed by imaging mineralized nodules (percentage surface area). Representative genes were selected for expression analyses, including cell proliferation (PCNA, Cdk2, p21, p53), differentiation (Runx2, Alpl, Bglap), oxidative metabolism (Catalase, GPX, MnSOD, CuZnSOD, iNos, Foxo1), DNA-damage repair (Gadd45), or apoptosis (Caspase 3). As expected, a high dose (200 centigrays), but not low doses, of either (sup 56) Fe or protons caused a loss of cancellous bone volume per total volume. Marrow cells produced mineralized nodules ex vivo regardless of radiation type or dose; (sup 56) Fe (200 centigrays) inhibited median nodule area by more than 90 percent at 5 weeks and 1 year post-irradiation, compared to controls. At 5 weeks post exposure, irradiation with protons or (sup 56) Fe caused few changes in gene expression levels during osteoblastogenesis, although a high dose of (sup 56) Fe (200 centigrays) increased levels of Catalase and Gadd45. In addition, supplementing cell culture media with SOD protected marrow-derived osteoprogenitors from the damaging effects of exposure to low-LET ((sup 137) Cs gamma) if irradiated in vitro, but had limited protective effects on high-LET (sup 56) Fe-exposed cells. In sum, exposure of mice to either protons or (sup 56) Fe at a relatively high dose (200 cGy) caused persistent bone loss, whereas only high-LET (sup 56) Fe increased expression of redox-related genes and inhibited osteoblastogenesis, albeit to a limited extent. We conclude that high-LET irradiation impaired osteoblastogenesis and regulated steady-state gene expression of select redox-related genes during osteoblastogenesis, which may contribute to persistent bone loss.

ionizing radiation↗

The Geothermal Artificial Intelligence for geothermal exploration

Exploration of geothermal resources involves analysis and management of a large number of uncertainties, which makes investment and operations decisions challenging. Remote Sensing (RS), Machine Learning (ML) and Artificial Intelligence (AI) have potential in managing the challenges of geothermal exploration. In this paper, we present a methodology that integrates RS, ML and AI to create an initial assessment of geothermal potential, by resorting to known indicators of geothermal areas namely mineral markers, surface temperature, faults and deformation. We demonstrated the implementation of the method in two sites (Brady and Desert Peak geothermal sites) that are close to each other but have different characteristics (Brady having clear surface manifestations and Desert Peak being a blind site). Here, we processed various satellite images and geospatial data for mineral markers, temperature, faults and deformation and then implemented ML methods to obtain pattern of surface manifestation of geothermal sites. We developed an AI that uses patterns from surface manifestations to predict geothermal potential of each pixel. We tested the Geothermal AI using independent data sets obtaining accuracy of 92-95%; also tested the Geothermal AI trained on one site by executing it for the other site to predict the geothermal / non-geothermal delineation, the Geothermal AI performed quite well in prediction with 72-76% accuracy.

15 GEOTHERMAL ENERGY↗

Characterizing the localization of organic C on mineral surfaces: a correlative microscopy/spectroscopy approach

It is estimated that organic carbon (OC) in soils exceeds the amount of OC in atmosphere and in vegetation pools combined.1 Given the current changes in climate and increasing temperatures in the environment, the fraction of OC sequestered in soils and sediments is more sensitive to decomposition and release as CO 2 in the atmosphere. Evidence implies that sorption and association of dissolved OC with inorganic soil components, i.e., soil minerals, is a key mechanism that contributes to stabilization and retention of OC in soil environment. Studies have shown a direct correlation between sorption of dissolved OC and soil mineral surface properties and their surface area. In addition, properties of organic compounds such as chemical structure and functional groups play a significant role in interaction of dissolved organic species with mineral surfaces. Association of OC with minerals via ligand exchange reactions, polyvalent tertiary bonding, or complexation with metal ions, is found to be preferential and dependent on the organic compounds’ functional groups.

54 ENVIRONMENTAL SCIENCES↗

Phosphorus recycling by mineral-catalyzed ribonucleotide cleavage on iron and manganese oxides

Abstract Phosphorus is an essential element influencing both food security via plant fertilization, and water pollution through excessive phosphorus use, yet the phosphorus cycle in ecosystems is poorly known. In particular, beyond adsorption, the role of iron and manganese oxides in catalyzing the abiotic dephosphorylation of biomolecules is debated. Here, we studied the reactions of ribonucleotides, containing different phosphate bonding, with goethite, hematite, and birnessite. We employed both high-resolution mass spectrometry of solution species and molecular modeling simulations of ribonucleotide-mineral complexes. Results disclose an up to fivefold preferential hydrolytic cleavage of a phosphoanhydride bond over a phosphoester bond, indicating that mineral-catalyzed reactions reflect the hierarchy reported for the activity of phosphatase enzymes. The fourfold higher catalytic reactivity of goethite and birnessite versus hematite is explained by mineral-specific binding rather than surface area differences. Corresponding simulated adsorbate conformations at the water–mineral interfaces are proposed. Overall, our findings provide new insights on the catalytic recycling of organic phosphorus species by mineral oxides.

58 GEOSCIENCES↗

VALENTInE: A Concept for a New Frontiers Class Long Duration In-Situ Balloon Mission to Venus

Venus and Earth are similar in bulk composition, size, density, and approximate distance from the Sun, yet Venus’s modern-day climate and surface geology is distinctly different [1]. Previous missions to Venus revealed unusual volcanic features, possible continental crust, widespread volcanic plains, a weak magnetic field [2], and insights into the Venusian atmosphere [3,4]. Unfortunately, data from these missions were limited in spatial and temporal resolution and global extent. A future mission to Venus is critical to address fundamental questions surrounding the chemical composition and dynamics of the Venusian atmosphere [5], its geologic history [6,7], its internal structure [8,9], and its habitability throughout time [10,11]. We present the Venus Air and Land Expedition: a Novel Trailblazer for In situ Exploration (VALENTInE) mission to meet this need. VALENTInE is a variable altitude balloon that will passively float in Venus’s atmosphere between 45 and 55 km altitude. VALENTInE will acquire atmospheric data at varying latitudes and longitudes in addition to mapping the surface geomorphology and mineralogy across multiple terrains. Mission Objectives: The VALENTInE mission concept is driven by four main science objectives: 1. Determine whether the driving force of the superrotation of Venus’s atmosphere is caused by horizontal or vertical momentum transport. 2. Determine whether the atmospheric composition and noble gas inventory of the Venusian atmosphere is a product of outgassing from the initial protoplanetary source or if there are significant contributions from exogenic sources. 3. Determine whether the tesserae regions (particularly Aphrodite Terra) are felsic and relatively older than surrounding regions. 4. Determine if there is any evidence of a recent dynamo preserved in the rock record of Venus. Mission Overview: A balloon architecture provides a robust system that can survive long-term in the Venusian environment while taking accurate measurements of the lower cloud deck and surface. Two prior balloon missions to Venus, VEGA 1 and VEGA 2 in 1984, have demonstrated the potential for such planetary exploration; however, these missions were short-lived (46 hr), with limited range (54 km). Our spacecraft concept consists of a battery powered balloon with a gondola and flyby carrier stage (Fig. 1). Our novel design allows for at least 15 days of atmospheric exploration, including multiple ascents and descents in the Venus atmosphere. VALENTInE is baselined to launch in 2032, cruise on solar power for 128 days, enter, descend, and inflate (EDI) into Venus’s atmosphere above Aphrodite Terra, and float in Venus’s atmosphere for a total nominal mission duration of 15 days. The balloon, able to control its altitude by changing its buoyancy, will make one full circumnavigation every 4–8 days and move poleward ~1 o latitude per day; it will be passively directed by the horizontal air currents on Venus. The balloon can only be controlled in the z direction, and the expected latitude range is ±10° from EDI. The balloon itself will be a tracer for atmospheric structures such as zonal winds [5, 12]. During the 15-day operational period, there will be five dips to 45 km for a compositional study of the lower atmosphere and geological and magnetic mapping of the surface. Dips are used to take images and measurements closer to the surface and to obtain in situ vertical atmospheric profiles between 45 and 55 km. Instruments: The VALENTInE instrument payload will allow for extensive study of the geology, atmosphere, and interior of Venus. The instrument suite consists of six instruments. The mission profile for each instrument is shown in Fig. 2. Lower Atmosphere Meteorology Analyzer (LAMA) is an atmospheric structure instrument consisting of a thermometer, barometer, and accelerometer to continuously measure temperature and pressure as a function of altitude, longitude, and latitude. TracE and Noble Gas Investigator (TENGI) is aneutral mass spectrometer used to sample the dense atmosphere. TENGI will operate continuously at 45 km and 55 km and will measure D/H ratios, as well as Ne, Ar, and O isotopic ratios. Kilometer Scale Spectral Imager (KSSI) is amultispectral imager (850-1150 nm) used to resolve surface features on the order of km. Near InfraRed Multispectral Photometer (NIRMP) is an Infrared (IR) photometer used to image the surface through the clouds to characterize mineral assemblages at five different areas of the surface. NIRMP will be operated during dwell. ELevation REConnaissance (ELREC) is a light detection and ranging (LIDAR) instrument used for measuring topography at five different areas of the surface. The ELREC data will be combined with those of NIRMP to determine mineral assemblages and how they correlate to topography. Magnetic Exploration and Interior Detective (MEID) is a magnetometer used to detect any near-surface magnetic anomalies. The magnetometer will continuously operate at all altitudes. Mission Design: The spacecraft’s propulsion system will have a wet mass of 930 kg and will be launched on an Atlas V rocket. The spacecraft will jettison the payload upon arrival in Venus’s atmosphere before decelerating to orbital velocity. Figure 2. Notional power-dip profile while the balloon is on the dayside. Risks and Challenges: Raising and lowering the spacecraft to dip beneath the haze layer require a large amount of energy. This issue was partly compensated by limiting the number of dips over the 15 day prime mission. Power needs for pumping helium are reduced by slowing the descent speed, which consequently increases spatial resolution of in situ measurements between 45 and 55 km. The main limitation for the duration of the mission is the need to carry 15 days’ worth of batteries. The bus experiences external Venusian temperatures ranging from ~27°C at 55 km altitude to ~110°C at 45 km altitude. These high atmospheric temperatures require thermal protection for the bus (instruments, electronics, and flight systems) during its descent, dwell at 45 km, and ascent. The bus is maintained at a mechanically safe temperature range of -10°C to 50°C using white external paint, multi-layer insulation (MLI), mechanical/thermal isolation (e.g. Ti, composites), and ~57 kg of Phase Change Materials (PCM). Images and spectra taken below the haze dominate the available data transmission regardless of the time spent at 45 km. Therefore, less time at the lower altitude mainly reduces the coverage of in situ measurements there. Further, we assumed an unrealistically low-density material for the helium storage tanks on the gondola. However, this issue is partially resolved if we were to jettison 75% of the spent helium storage tanks. After the entry process, the balloon volume remains mostly inflated and storage tanks are required only for reducing balloon volume in dipping to 45 km. This mission was planned against an expected New Frontiers 5 (NF5) cost cap of $1B, as the NF5 call had not yet been released. The mission we describe fits within the predicted cost cap if the flyby carrier stage, responsible for powering the spacecraft during cruise and for relaying in situ measurements back to Earth, can be contributed by another space agency. Acknowledgments: We thank the JPL Planetary Science Summer School, especially A. Nash, J. Scully, K. Mitchell, L. Lowes, and J. Armijo, and our mentors from JPL Team X. Thank you to our review panel for their insightful review. References: [1] Kane, S. et al. (2019) JGR:Ps, 124 , 2015–2028. [2] Phillips, J. L., & Russell, C. T. (1987). JGR: Space Physics , 92 (A3), 2253-2263. [3] Nakamura, M. et al. (2018) Earth Planets Space, 70 (1), 144. [4] Svedhem, H. et al. (2009) JGR:P 114 (E5). [5] Limaye et al. (2009) Decadal Survey White Paper . [6] Ivanov, M. and Head, J. (2011) PSS, 59 (13) , 1559-1600. [7] Smrekar, S. et al. (2018) Space Sci Rev, 214 (5), 88. [8] O’Rourke, J. et al. (2018) EPSL, 502 , 46-56. [9] O’Rourke J. et al. (2019) GRL , (46), 5768–5777 [10] Way, M. et al. (2016) GRL, 43 (16), 8376-8383. [11] Way, M. et al. (2020) JGR:P, 125 (5), e2019JE006276. [12] Preston, R. A. et al. (1986) Science, 231 (4744), 1414-1416.

Mission Concept↗

Comprehensive parametric study of CO 2 sequestration in deep saline aquifers

Carbon dioxide injection in deep saline aquifers is a key method for permanently sequestering anthropogenic CO 2 . Here this study employs a reactive transport model to explore mineral precipitation/dissolution and its impact on reservoir properties in deep saline aquifers. We also assess capillary pressure and relative permeability hysteresis on various CO 2 trapping mechanisms. Results from this study reveal the significant influence of initial brine composition on mineral precipitation/dissolution. The dissolution and precipitation of minerals have different effects around the wellbores compared to the overall reservoir. Additionally, salt concentration (Ca ++ and Mg ++ ) and quartz surface area affect CO 2 mineralization, while Na + impacts halite precipitation, altering flow properties. The effect of capillary pressure is significant, as including the capillary pressure in the simulation case resulted in significantly improved CO 2 trapping, achieving almost total dissolution of the injected CO 2 in around 300 years. This study offers novel insights into the interactions of reservoir minerals, brine properties, and the injected CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Interfacial Smoothing and Dissolution during Unconventional Reservoir Stimulation Implications for Hydrocarbon Mobilization and Transport

Hydraulic fracturing of low-permeability rocks significantly enhances hydrocarbon production from unconventional reservoirs. However, fluid transport through low-permeability rocks, and the influence of geochemical transformations on pore networks, are poorly constrained. Mineral reactivity during interactions with injected water may alter the physical nature of the rock, which may affect hydrocarbon mobility. To assess alteration to the rock, we previously conducted a hydrothermal experiment that reacted cubed rock samples (1 cm3) with synthetic hydraulic fracturing fluid to simulate physicochemical reactivity during hydraulic fracturing. We analyzed unreacted and reacted rocks by small-angle neutron scattering and high-pressure mercury intrusion to determine how nanoscale (~1-1400 nm) pore networks of unconventional reservoir rocks are influenced by reaction with hydraulic fracturing injectates. We show that fluid-rock interactions have a two-fold influence on hydrocarbon recovery, promoting both hydrocarbon mobilization and transport. Pore-matrix interfaces smooth via removal of clay mineral surface asperities, reducing available surface area for hydrocarbon adsorption by ca. 12-75%. Additionally, hydraulic fracturing fluid-induced dissolution creates new pores with diameters ranging in size from 800-1400 nm, increasing the permeability of the rocks by a factor of 5-10. These two consequences of mineral dissolution act in concert to release hydrocarbons from the host rock and facilitate transport through the rock during unconventional reservoir production.

Herz-Thyhsen, Ryan↗

Ectopic bone formation by marrow stromal osteoblast transplantation using poly(DL-lactic-co-glycolic acid) foams implanted into the rat mesentery

Porous biodegradable poly(DL-lactic-co-glycolic acid) foams were seeded with rat marrow stromal cells and implanted into the rat mesentery to investigate in vivo bone formation at an ectopic site. Cells were seeded at a density of 6.83 x 10(5) cells/cm2 onto polymer foams having pore sizes ranging from either 150 to 300 to 710 microns and cultured for 7 days in vitro prior to implantation. The polymer/cell constructs were harvested after 1, 7, 28, or 49 days in vivo and processed for histology and gel permeation chromatography. Visual observation of hematoxylin and eosin-stained sections and von Kossa-stained sections revealed the formation of mineralized bonelike tissue in the constructs within 7 days postimplantation. Ingrowth of vascular tissue was also found adjacent to the islands of bone, supplying the necessary metabolic requirements to the newly formed tissue. Mineralization and bone tissue formation were investigated by histomorphometry. The average penetration depth of mineralized tissue in the construct ranged from 190 +/- 50 microns for foams with 500-710-microns pores to 370 +/- 160 microns for foams with 150-300-microns pores after 49 days in vivo. The mineralized bone volume per surface area and total bone volume per surface area had maximal values of 0.28 +/- 0.21 mm (500-710-microns pore size, day 28) and 0.038 +/- 0.024 mm (150-300-microns, day 28), respectively. As much as 11% of the foam volume penetrated by bone tissue was filled with mineralized tissue. No significant trends over time were observed for any of the measured values (penetration depth, bone volume/surface area, or percent mineralized bone volume). These results suggest the feasibility of bone formation by osteoblast transplantation in an orthotopic site where not only bone formation from transplanted cells but also ingrowth from adjacent bone may occur.

NASA Discipline Developmental Biology↗

Reactive Transport Modeling of Hydrogen Production from Serpentinization of Olivine

Hydrogen production from serpentinization of ultramafic rocks represents a promising natural pathway for generating carbon-free energy, yet its kinetics and controlling factors remain incompletely understood. A key challenge in advancing serpentinization research lies in the heterogeneity of porosity and permeability in rocks, which leads to nonuniform fluid velocity fields, as well as uncertainties in estimating reactive surface area and identifying appropriate mineral reaction equilibria. Additional complexities arise from the role of dissolved SiO 2 , Fe 2+ /Fe 3+ partitioning, and the limited effect of pH variations within the strongly alkaline regime on hydrogen yields. These challenges hinder straightforward extrapolation from laboratory tests to practical applications of hydrogen production from natural rocks. Here, in this work, we address these questions using a simulation-based reactive transport modeling framework calibrated against controlled laboratory experiments reported elsewhere. The model couples geochemical kinetics, multiphase flow, and mineralogical feedbacks, enabling systematic evaluation of how surface area, dissolved silica concentration, Fe redox state, temperature, and pressure govern serpentinization and H2 generation. We find that surface area exerts the strongest control on reaction rates and hydrogen yields, while Fe 2+ /Fe 3+ ratios act as secondary modulators. Elevated dissolved silica concentrations suppress hydrogen production but accelerate serpentine precipitation, whereas increasing pH beyond 12 within the strongly alkaline regime produces only marginal gains. Finally, we demonstrate that integrating targeted experiments with calibrated simulations offers a powerful and efficient approach for predicting hydrogen yields and assessing parameter trade-offs in industrial-scale applications. This integration can substantially reduce the experimental burden while improving predictive capability, thereby enhancing both the mechanistic understanding and the practical feasibility of hydrogen production from serpentinization.

08 HYDROGEN↗

Spatial heterogeneity analyses of pore structure and mineral composition of Barnett Shale using X-ray scattering techniques

The spatial heterogeneity of pore structure and mineral composition at mu m to mm scales in mm to cm-sized shale samples complicates the laboratory measurements of porosity & pore size distribution and consequently reservoir quality evaluation. Traditional fluid invasion characterization methods typically take hours to days to get data and can only test relatively small samples (usually 2.54 cm diameter core plugs and mm-sized rock chips). Furthermore, the Xray scattering techniques at the Advanced Photon Source of the Argonne National Laboratory have the capability to non-destructively determine the pore structure and mineral composition of mm x mm area in a short time of seconds and to hold several to hundreds of mm 2 sized sample to conduct large area heterogeneity analysis in the short duration of hours. With the use of ultra-small angle X-ray scattering (USAXS), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS), the porosity, surface area and pore size distribution of two Barnett Shale samples have been mapped out and the mineral compositions are determined qualitatively. Overall, the porosity and pore surface area of the Barnett Shale Sample A over a 36 cm2 area ranges from 1.70 % to 8.13 % and 8.87 m 2 /g to 40.2 m 2 /g respectively. The porosity and surface area of Sample B over a 24 cm 2 area varies from 3.15 % to 11.7 % and 18.3 m 2 /g to 60.2 m 2 /g. In Sample A, the mineral composition shows a shift from carbonate-rich to siliciclastic-rich over a distance of several millimeters. For Sample B, the mineral compositions are mainly siliciclastic and do not show an obvious lithological change. The direct observations of high spatial heterogeneity of pore structure and mineral composition in shale illustrate the utility of integrated X-ray scattering techniques to provide valuable insights into shale studies and reservoir evaluation.

58 GEOSCIENCES↗

An Evaluation of AI Models’ Performance for Three Geothermal Sites

Current artificial intelligence (AI) applications in geothermal exploration are tailored to specific geothermal sites, limiting their transferability and broader applicability. This study aims to develop a globally applicable and transferable geothermal AI model to empower the exploration of geothermal resources. This study presents a methodology for adopting geothermal AI that utilizes known indicators of geothermal areas, including mineral markers, land surface temperature (LST), and faults. The proposed methodology involves a comparative analysis of three distinct geothermal sites—Brady, Desert Peak, and Coso. The research plan includes self-testing to understand the unique characteristics of each site, followed by dependent and independent tests to assess cross-compatibility and model transferability. The results indicate that Desert Peak and Coso geothermal sites are cross-compatible due to their similar geothermal characteristics, allowing the AI model to be transferable between these sites. However, Brady is found to be incompatible with both Desert Peak and Coso. The geothermal AI model developed in this study demonstrates the potential for transferability and applicability to other geothermal sites with similar characteristics, enhancing the efficiency and effectiveness of geothermal resource exploration. This advancement in geothermal AI modeling can significantly contribute to the global expansion of geothermal energy, supporting sustainable energy goals.

Energy & Fuels↗

Identifying the mechanisms of cation inhibition of phenol oxidation by acid birnessite

Abstract Many phenolic compounds found as contaminants in natural waters are susceptible to oxidation by manganese oxides. However, there is often variability between oxidation rates reported in pristine matrices and studies using more environmentally relevant conditions. For example, the presence of cations generally results in slower phenolic oxidation rates. However, the underlying mechanism of cation interference is not well understood. In this study, cation co‐solutes inhibit the transformation of four target phenols (bisphenol A, estrone, p ‐cresol, and triclosan) by acid birnessite. Oxidation rates for these compounds by acid birnessite follow the same trend (Na + > K + > Mg 2+ > Ca 2+ ) when cations are present as co‐solutes. We further demonstrate that the same trend applies to these cations when they are absent from solution but pre‐exchanged with the mineral. We analyze valence state, surface area, crystallinity, and zeta potential to characterize changes in oxide structure. The findings of this study show that pre‐exchanged cations have a large effect on birnessite reactivity even in the absence of cation co‐solutes, indicating that the inhibition of phenolic compound oxidation is not due to competition for surface sites, as previously suggested. Instead, the reaction inhibition is attributed to changes in aggregation and the mineral microstructure.

Balgooyen, Sarah↗

A 2-million-year-old ecosystem in Greenland uncovered by environmental DNA

Late Pliocene and Early Pleistocene epochs 3.6 to 0.8 million years ago had climates resembling those forecasted under future warming. Palaeoclimatic records show strong polar amplification with mean annual temperatures of 11–19 °C above contemporary values. The biological communities inhabiting the Arctic during this time remain poorly known because fossils are rare. Here we report an ancient environmental DNA (eDNA) record describing the rich plant and animal assemblages of the Kap København Formation in North Greenland, dated to around two million years ago. The record shows an open boreal forest ecosystem with mixed vegetation of poplar, birch and thuja trees, as well as a variety of Arctic and boreal shrubs and herbs, many of which had not previously been detected at the site from macrofossil and pollen records. The DNA record confirms the presence of hare and mitochondrial DNA from animals including mastodons, reindeer, rodents and geese, all ancestral to their present-day and late Pleistocene relatives. The presence of marine species including horseshoe crab and green algae support a warmer climate than today. The reconstructed ecosystem has no modern analogue. The survival of such ancient eDNA probably relates to its binding to mineral surfaces. Our findings open new areas of genetic research, demonstrating that it is possible to track the ecology and evolution of biological communities from two million years ago using ancient eDNA.

58 GEOSCIENCES↗

Development of Methods of Characterizing Coal in Its Plastic State

Coal in its plastic state (typically 400-460 C) was examined by the isothermal Gieseler plastometry of seven selected coals of widely varying plastic properties. Kinetic models were proposed for the isothermal plastometric curves. Plastic behavior was compared with a variety of laboratory analyses and characterizations of these coals, including classical coal analysis; mineral analysis; microstructural analysis (extractable fractions, surface area measurement, and petrographic analysis); and thermal analysis (thermogravimetric analysis, thermomechanical analysis, and differential scanning calorimetry). The phenomenon of a sharp, large, poorly reproducible exotherm in the differential scanning calorimetric analysis of coking coals was examined. Several coal extrudates show mineral distribution, organic maceral composition and overall calorific value to be little affected by 800 F extrusion. Volatile matter and plastic properties are moderately reduced, and the network structure (as gauged by extractables) appears to be slightly degraded in the extrusion process.

Lloyd, W. G.↗

Influence of Clay Wettability Alteration on Relative Permeability

Abstract Understanding the wettability of porous materials is important to model fluid flow in the subsurface. One of the critical factors that influences wetting in real reservoirs is the composition of geologic materials. The wetting properties for clay minerals can have a particularly strong impact on flow and transport. In this work, we analyze the chemical composition of a Mt. Simon sandstone core to resolve the microscopic structure of clay regions and assess how alterations to the local wetting properties influence multiphase transport based on core flooding experiments and relative permeability simulations. We show that whichever fluid has greater affinity toward clay minerals will tend to accumulate within these high surface area regions, leading to dramatic shifts in the relative permeability. This work establishes the essential importance of the mineral composition and associated wetting properties in the modeling of flow and transport in reservoir‐scale systems.

Fan, Ming↗

Detection of hydrothermal alteration at Virginia City, Nevada using Airborne Imaging Spectrometry (AIS)

Airborne Imaging Spectrometer (AIS) data were collected over Virginia City, Nevada; an area of gold and silver mineralization with extensive surface exposures of altered volcanic rocks. The data were corrected for atmospheric effects by a flat-field method, and compared to library spectra of various alteration minerals using a spectral analysis program SPAM. Areas of strong clay alteration were identified on the AIS images that were mapped as kaolinitic, illitic, and sericitic alterations zones. Kaolinitic alteration is distinguishable in the 2.1 to 2.4 and 1.2 to 1.5 micrometer wavelength regions. Montmorillonite, illite, and sericite have absorption features similar to each other at 2.2 micrometer wavelength. Montnorillonite and illite also may be present in varying proportions within one Ground Instantaneous Field of View (GIFOV). In general AIS data is useful in identifying alteration zones that are associated with or lie above precious metal mineralization at Virginia City.

Hutsinpiller, A.↗